Hydraulic cement composition and indurating composition therefor



lot-ss- "relates to such compositions scale and deteriorate very improved somewhat in 4 'its resistance to freezing and thawing and in its Patented Apr. 22, 1952 I I I 4..

HYDRAULIC 5 Edward W. Scripture,

Ohio, assignor to The Ross Ram-12E;

PA-TENT";

' essence I 1 1 e CEMENT COMPOSITION AND INDURATING comrosrrron rnsnsron Jr., Cleveland Heights, Master Builders Company, Cleveland, Ohio, a corporation of Ohio tion November 17, 1948,

Serial No. 60,635

9Claims. (CL10612) .This invention relates to hydraulic cement compositions such as concrete or mortar, and the like,"and to indurating compositions for addition to concrete or mortar mixes. It especially and mixes containing a plasticizing and ir ainin agent which perm of structures prepared from such compositions.

, One of the objectives in the cement industry for many years. has been to develop a concrete which would have greater resistance to the destructive effects of freezing and thawing, when ing the formation of laitance on exposed to the weather, and especially to the extremely destructive effects on pavements when salts, such as calcium chloride and sodium chlo-- ride, are used for de-icing. Calcium chlgride, for

instance, is frequently mixed with sand and scattered on the highway to melt of ice and snow. Concrete pavements made according to the usual methods and with the usual materials tend to rapidly when so treated. Concrete can be resistance to scaling when treated with calcium chloride by the use of richer mixes or drier mixes,

. and by improved methods of placing and finishing, but such means have not provided a solution to the problem.

It is an object of this invention to provide a cement composition or an indurating composition for cement mixes comprising ingredients which entrain air in the concerete and which markedly increased the plasticity of their concrete.

It is a further object of this invention to produce a concrete of generally improved properties,

and particularly of enhanced resistance to repeated freezing and thawing, ,to provide means whereby concrete, of improved resistance to freezing and thawing may be produced, and to provide cement and concrete produced therefrom exhibiting increased resistance to successive freezing and calcium chloride, agents.

It is a further object of this'invention to pro vide cement and concrete ofimproved resistance to freezing and thawingwhich retain their other common salt, and similar desirable properties unimpaired, and to improve cement and concrete in these respects without decreasing strength and structural value.

Other objects and advantages of the invention will become apparent asthe description proceeds. It has been found in .recent years that a very marked increase in the resistance of concrete to A freezing and thawing and in its resistance to scaling on de-icing with calcium chloride and the like can be produced by the entrainment of l a1 improvement in the durability i1;

thawing in the presence of.

air in the concrete mix. This air is entrained in 4 the concrete in the form of small, discrete spheroids, and it is thought that these small, discrete spheroids, being totally enclosed within the 5 cement matrix, do not completely fill with water when the concrete is wet and so provide a cushion to minimize the effects of the disruptive forces of freezing and thawing. Also, the incorporation of this entrained air tends to make the mix more 10 fatty and cohesive so that its tendency toward a bleeding is reduced. By reducing the bleedthe surface of the concrete, which is one of the causes of scaling, is more or less prevented. In the practice of air entrainment to improve the resistance of concrete to freezing and thawing and to plasticize the mix, it is desirable to duce an air content in pr 2| a e y e een h /nand fi-%-byvolume the'coifirete.

to 21'%"6f air in mortar which oes l a ear con nt of the concreteisT'not as high as 3% by volume, the full benefits of air entrainment. are not realized. One the other hand, if the air content of the concrete ris s above about 5% or 6% b vol losses in strengt are pro need the prec1a mcrease. ur

will entrain air in cement; man terials ticularly surface t unc ion. Most such materials, however, have certain deleterious effects on cement mixes. They will interfere with the setting or hardening of the cement; they will cause the cement to have low and undesirable flexural and compressive strengths; they will entrain entirely too much or too litle air; and generally they will have a plurality of these defects.--

It has been the practice heretofore to consider that the adverse effects of these reagents were necessary in order to have the advantages of air entrainment. Air-entraining reagents in use are more or less of a compromise in providing a substantial proportion of the obtainable benefits of air entrainment without too greatly interfering with other desirable properties in, the cement.

It is an object of the present invention to'provide a method of entraining air in concrete and mortar mixes, wherein one may obtain the equivalent of between 3% and 6% air content (by volume) in cre andwhereiii the concrete and mortar produced has compressive and ,flexural strengths which are not only not appreciablv decreased but are improved over that I obtained when air. is not entrained the cement.

q EXAMlNEB without in a ility. rehas'nerbe" was to find materials which gLlVG ager ts will accomplish I have found that a certain class of com-- It is another object of the present invention to provide a material which may be incorporated in cement mixes to greatly increase resistance to freezing and thawing without reducing the compressive strength of the article produced therefrom.

It is another object of the present invention to provide such a material that is compatible with cement dispersing agents, such as calcium TEE? lignin su phg pounds, namely the mononuclear .aryl sulfonates which are surface act ve in that they lowerthe u e.iensioaefnwatet wil when .us w y small quantities entrain a desired amount ofai;

in concrefglal'idlthus greatly increase its resistance tofreezing and thawing without reducing compressivestreng'th. "I have also found that these materials are not only compatible with cement dispersing agents, but when mixed with these materials, such for example as calcium lignin sulfonate, provide enhanced air entrainment. The other qualities, including flexural and structural strengths, are not only not reduced but are greatly increased.

The mononuclear alkyl aryl sulfonates or alkylphenyl sulfonates, which function as above-described in cement mixes, may be designated by the following general formula,

where R; is an alkyl radical containing nine or ten to sixteen or eighteen carbon atoms, preferably in the form of a single long chain, and M is a univalent basic radical such as an alkali metal, including sodium, potassium, ammonium and triethanolamine radicals.

The alkylphenyl sulfonate is usually manufactured by a process such that it contains a considerable percentage of sodium sulfate, but in the proportions in which these air entraining agents are used, this sodium sulfate is not injurious to the concrete and it is not necessary to separate the alkylphenyl sulfonate from the sodium sulfate.

1- have found that particularly desirable mononuclear alkylaryl sulfonates are sodium and potassium dodecylphenyl sulfonates and mixtures of alkylphenyl sulfonates'having an average molecular weight, which indicates that the alkyl groups have an averageof about twelve or ten to fourteen carbon atoms. Usual processes of manufacture start with raw materials of mixed molecular weight so that commercially available alkylphenyl sulphonates are mixtures of compounds having different molecular weights.

The alkylphenyl sulfonate may be added to a concrete or mortar mix in the form of a liguid a paste, or a dry powder, whichever is more convenient and rhoreecofiomical. It will be apparent that the alkylphenyl sulfonate may be added to the cement at any time or ground with the cement at the time of manufacure of the cement. The alkylphenyl sulfonate alone or Q combined with the other ingredients of the compositions of my invention may be added to the cement, to the aggregate, to the water, or to any As little as .0005%, based on the weight of the cement, of the mononuclear alkylaryl sulfonate is noticeably effective in increasing the air content of a mortar or concrete mix and improving the properties of the products produced therefrom. An amount of such compound greatly in excess of 0.1% will cause the entrainment of an excessive amount of air. The amount of alkylphenyl sulfonate preferably used is about .00l% to .005 based on the weight of the cement, but with some cements and some concrete mixes it may be desirable to use amounts either above or below these quantities.

When in accordance with the preferred aspect of the present invention the quality of the cengrete is further improved by the addition of a nement. dimersinaa llt "silcfii e5 daT'lum llgnm sulfonate from waste sulflte liquor, I have found that the most desirable proportions of such dispersing agents to be used are from .1% to 2% to about 35%- or .5%, by weight of the cement. These quantities of dispersing agent combined with one or more of the aforementioned mononuclear alkylaryl sulfonates substantially improve the quality of the concrete, especially with respect to the compressive and flexural strengths.

It is sometimes desired to increase the rate of hardening of the concrete, and for this purpose an accelerator may be used. Qalcium c hloride is a readily available and an inexpensive ac- ,celerating agent. The desirable proportions of accelerator are usually between .1% to 2% or 2.5%, by weight of the cement. Additional ingredients, such as fly ash and other finely divided materials, may be present in the concrete with the air entraining agent to improve workability or provide pozzuolanic action. If it is desired to increase the ultimate strength of the concrete or mortar, it may be desirable also to incorporate a derivative of benzoic acid, such as set forth in one or more-"of the United States Patents Nos. 2,264,336, 2,360,517, 2,360,518 and 2,360,519. The preferred derivative of benzoic acid is salicyclic acid or a salt thereof.

It is of interest to note that these alkylphenyl sulfonates, although they give a good but dispersed foam, do not give as good a foam under many conditions as that produced by other surface tension reducing agents such as the alcohol sulfates, and the foams pfoduced with these alkylphenyl sulfonates do not resist high temperatures but in concrete mixes the foam-forming action of the alkylphenyl sulfonates is enhanced by the alkali of the concrete. Since concrete is mixed and used at normal temperatures. the temperature stability of the foam is of no importance. Hence the alkylphenyl sulphonates are peculiarly adapted for entraining air in concrete mixes.

The increase in the entrained air content and greatly improved resistance to freezing and thawing. accompanied by improvements in strength, securable with alkylphenyl sulfonates, whether used in the form of powder, paste or liquid, will be seen from the following examples.

Example 1 Mortar mixes of cement and standard sand were made and tested in accordance with the tentative method of test for air content of air entraining Portland cement mortar (ASTM Designation C-47T). From this same mortar 2" x 2" cubes were made and tested for compressive strength at the ages of 1, 7 and 28 days. In mix No. 1, which served as the concross REFEREi-ZSE Y EXAMINER trol, no addition was made. In mix No. 2.

-.0025% alkylphenyl sulfonate was added in the form or a liquid containing 20% of the active ingredient. In mix No. 3, .0025% alkylphenyl ent amounts of alkylphenyl sulionateused in conjunction withcalcium lignosulfonate dispersing agent and calcimn chloride, two series of tests were made. In the first series or tests cement (AS'I'M Designation 0175-471) call for an air content of mortar prepared and tested in accordance with Method C185 of 18:3% by volume. It will further be noted that the amount-of water required for a given flow, as 65 usually with air entraining cements or air en- 70 training agents compressive strengths are decreased.

Example 2 To show the efiects of the addition. of differ- 75.

sulionate was added in the form of a paste con- 5 a control mix, No. 1, with no addition was made ta n 2 active ingredient. and in mix N0. 4, with 5 sacks of cement per cu. yd. In mix No. .0024% alkylp enyl sulfonate was added in the 2 the cement dispersing agent and calcium chloform of a dry powder containing 40% active inride were added in suitable proportions to a gredient. All these percenta e a e b d on the concrete mix having approximately 4% sacks of weight of the cement. The pertinent data, in- '10 cement per cu. yd. In mixes Nos. 3 and 4,'with cluding the m n of ingredients added. the approximately 4%,sacks of cement per cu. yd., percentage of active ingredients added, the per- 'the alkylphenyl sulfonate was added in the procent of ntr in air y V lum 0! he portions 0! .001% and .002% of the cement'by the water-cement ratio by weight, and the comweight, respectively. All the mixes in this P iv Strengths a the ages of test, in Pounds series were made to slumps between 4" and -5" per sq. in., are shown in the followingtable: and the percentages of entrained air were determined by means of the Klein-Walker air 1 a 4 meter. In the second series, made at another 1 time, the control mix, No. 5, was again made AlkylAryl Bulphonate with 5 sacks of cement per cu. yd. and the three i 1 Added mixes with additions, Nos. 6, 7 and 8 were made with approximately 4% sacks of cement per fgfg gg'g 3325 cu. yd. In mix No. 6 the calcium lignosulfonate and calcium chloride were added without air en- Amount added-percent.-. None .0125 .010 .000 raining agent. In mixes Nos. 7 and 8 the Egg? agi 353132: 3 3 3 alkylphenyl sulfonate was added in the propor- Water-Cementratio by wt... .767 .000 .000 .000 tions of .001% and .002% by weight of the $fiii strengflh cement, respectively. The air contents were 1 day 100 250 200 again determined by means of the Klein-Walker QEZiQIIIIIZIII: 51% $3323 it? $1328 air meter. The slumps for this series 0: mixes were all between 2" and 3". The results of .both It will be seen that with no addition the morseries 0: mixes are shown in the following tar entrains only 4% of air, but with the alkyltabulation:

Material Added, percent I)?" l V Sod'i D Water- 05653;? i g $51 Dispers- Calcium um Cement per c 65 cent .ing Agent Chloride if ggggg (3527:3221:

SERIES 1 SERIES 11 f .23 .2 s is .20 v .10 .001 0.00 420 2 0.3 .20. .10. .002 0.41 4.25 2% 1.3

phenyl sulfonate added, approximately in the 55 It will be noted that whereas the calcium proportion of .0025% by weight of the cement. lignosulfonate dispersing agent entrains more air the entrained air content is increased to from than is entrained in the control mix, additional 16.1% to 18.6% with the addition of this reair is entrained by the successive additions of agent in the three different forms. The tentaincreasing amounts of the allqrlaryl sulfonate. tive specifications for air entraining Portland Example 3 In order to determine the effects of varying quantities of alkylphenyl sulfonate on the proper# ties of concrete, particularly the amount of air entrained and the compressive strength, two series of mixes were made up with varying proportions of alkylphenyl sulfonate combined with calcium lignosulfonate and calcium chloride. All the mixes were made with a nominal cement factor of 6 sacks per cu. yd. and a nominal slump of 3". Determinations were made of the amount of water required for the same consistency, of the amount or air entrained, and of the compressive strengths. at two ages. The specimens iron the 7. first series. were used to determine the strengths at 28 days, and those from thesecond series strengths at 1-day. These concrete mixes consisted of cement, sand, and crushed lime- 8 Ezample4 To determinethe effect of the entrainedain'on the resistance of concrete to freezing and thawing, concrete mixes were made up in a mixer and stone. They were made in a concrete mixer a 5 concrete'beams for the. freezing and thawing .tests e e eontents were determmed were made from these mixes in accordance with Wlth a Elem-Walker mete! and eylmdels for standard methods. Concrete cylinders were also compressive strength were made and broken acmade fro the same mixes compressive cording to standard methods. In each series the strength t i ti After the cylinders'had 1 and was made wltheut any been cured 28 days they were broken in a comaddition, the second m x, Nos. 2 and 7, wl h pression machine. In the first series of mixes the i 11gnu1fnate dlspelsmg agent, and concrete beams were cured for 28 days and then 61131111 ehlerlde, and the third, fourth and fi subjected to alternate freezing and thawing in an mlxes, 3, 5 and 9, and 10, Wlth apparatus which produced 12 cycles of freezing the same quantlties of dispersing agent and cal- 15 and thawing per day The beams f m the cium chloride but with increasing quantities of d Series were cured days and t subje ted ailkylphenyl sulfonate Data Secured in es to the alternate cycles of freezing and thawing. tests are shown in the following table: The first series of mixes was made with a nominal Material Added, Per Cent 0 0 m p r as s i T e Air gtrength, Lbs. Mix N'r. Sodium Water- 2 Per Dispersing Calcium Dcdecyl- Cement c 6 Cent Agent Chloride phenyl Ratio,

sulfonate Gals/sack 28 Days 1 Day 0 SACKS PER CUBIC YARD It will beseen that the addition of dispersing agent produces small increases in entrained air, but these are greatly increased by the inclusion of alkylphenyl sulfonate in the mix and the amounts of entrained airincrease with increasing proportions of alkylphenyl sulfonate. It will be noted also that the amount of water required for a given consistency is greatly decreased when the dispersing agent and alkylphenyl sulfonate are used. Contrary to the general expectation with most air entraining agents, when the air content is greatly increased, compared with the control mix, the strengths of the mixes with considerable proportions of entrained air. still show increases in strength, both at 1-day and at 28-days. Even with air contents between 5% and 6% by volume of the concrete, the mixes with dispersing agent and alkylphenyl sulfonate still show strengths higher than those of the corresponding control mixes.

cement factor of 6 sacks per cu. yd. and a nominal slump of 4". The second series of mixes was per cu. yd. and a nominal slump of 4''. In the first series, mix No. 1 was the control with no addition. Mix No. 2 was made with the addition of dispersing agent and calcium chloride but no alkylphenyl sulfonate. Mixes Nos. 3 and 4 were made with the same addition of alkylphenyl sulionate as well as dispersing agent and calcium chloride but with a smaller proportion of calcium chloride. In the second series mixes Nos. 5, 6, 7, and 8 correspond to mixes Nos. 1, 2, 3, and 4, respectively, of the first series. The following table shows the additions to each mix, the watercement ratio required for the same slump, the percent, of air entrained, the compressive strength at 28 days, and the number of cycles of freezing and thawing which produced a substantial decrease in the dynamic modulus of elasticity E, as determined by a sonic method of test.

Material Added, Per Cent Compressive Per Air, No. 0! Mix No. Sodium Water- Per gj fg Cycles Dispersing Calcium Dodecyl Cement Cent P 6: T in E Agent Chloride phenyl Ratio, p Sulphonste Gals/sack 6 SACKS-SLUMP 4 INCHES l O 0 0 5.91 1.1 4,360 40 38 25 25 O 5. 23 2. 9 5, 390 31 25 25 001 5. 06 5. 3 4, 780 182 25 25 15 001 5. 00 5. 2 5,330 21 5 SACKS-SLUMP 4 INCHES made with a nominal cement factor of 5 sacks CROSS REFERZKQE It will be noted that in comparison with the plain mix in each series the mixes with cement dispersing agent, with and without alkylphenyl sulfonate, show substantial reductions in the water required for a given consistency. Likewise, in all cases these mixes show substantial in-; creases in strength over the corresponding control mixes. In both series the mixes, Nos. 2 and 6, with cement dispersing agent and calcium chloride only, show some increase in air content over the control mixes with no additions. In mixes Nos. 3 and 4 of series I, and mixes Nos. '7 and 8 of series II, the addition or alkylphenyl sulfonate further increases the entrained air content. All of the mixes with cement dispersing agent and with alkylphenyl sulfonate show substantial increases in their resistance to freezing and thawing, as indicated by the losses in dynamic E and the number of cycles of freezing and thawing required to produce these losses. Whereas the cement dispersing agent and calcium chloride alone give substantial increases in resistance to freezing and thawing, these are greatly enhanced by the addition of the alkylphenyl sulfonate and the entrainment of more air.

The Portland cement utilized in the above examples may be substituted by other hydraulic cements. The quantities of the ingredients may be varied or the aggregates may be omitted entirely in accordance with the usual practices as recognized by those skilled in the art. The sodium dodecylphenyl sulfonate may be substituted by any one or more of the alkali metal (including ammonium and triethanolamine) salts of alkylphenyl sulfonic acids having 9 to 18 carbons in the alkyl group, although as above stated mixtures of sulfonates having an average of 12 carhens in the alkyl group are preferred.-

Furthermore, the inclusion of other materials in the concrete or mortar mixes or in the compositions claimed which are known to have beneficial efiects on the resultant product, such as finely divided pozzuolanic or inert powders, and derivatives of benzoic acid, such as salicylic acid, may be included in these mixes and compositions or in the cement without departing from my invention.

Furthermore it is to be understood that the particular form of product shown and described and the particular procedure set forth are presented for purposes of explanation and illustration, and that various modifications of said product and procedure can be made without departing from my invention as defined in the appended claims.

What I claim is:

1. A dry hydraulic cement containing .001% to .005%, based on the weight of the cement, of an alkylphenyl sulionate containing about 9 to 18 carbon atoms in the alkyl group.

2. A dry hydraulic cement containing .001% to .005%, by weight of the cement, of a salt of a univalent base and alkylphenyl sulfonic acids having an average of about 10 to 14 carbon atoms in the alkyl' groups.

3. A dry hydraulic cement according to claim 1 which also contains a calcium ligno sulphonate dispersing agent in the proportions of .l% to .5% of the weight of the cement.

4. A dry hydraulic cement in accordance with claim 1 containing calcium lignin sulfonate dried from waste sulfite liquor in the proportions of .l% to .5% of the weight of the cement.

5. An hydraulic cement concrete or mortar mix containing a water-soluble alkylphenyl sulfonate in the amount of .001% to .005%. by weight of the cement, said alkylphenyl sulfonate containing 9 to 18 carbon atoms in the allwl group.

6. An hydraulic cement concrete or mortar mix according to claim 5 containing a calcium ligno sulphonate dispersing agent in the amount of .l% to .5% of the weight of the cement.

7. The mix according to claim 6 in which the cement dispersing agent is calcium lignin sulfonate.

8. An indurating composition for hydraulic cement mixes comprising in combination an alkylphenyl sulfonate and a calcium ligno sulphonate dispersing agent, said ingredients being proportioned to provide when added to cement .l% to .5%, based on the weight of the cement, of said I cement dispersing agent, and at the same time .001% to .005%, by weight of the cement, of said alkylphenyl sulfonate, said alkylphenyl sulfonate being a monovalent base salt of an alkylphenyl sulfonic acid having 9 to 18 carbon atoms in the alkyl group.

9. The indurating composition of claim 8 in which the cement dispersing agent is calcium lignin sulfonate, and in which there is present a plurality of alkylphenyl sulfonates having an average of about 12 carbon atoms in the alkyl group.

EDWARD W. SCRIP'I'URE, Jx.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Bowman 

